Application of high toughness, low viscosity nano-molecular resin for reinforcing pothole patching materials in asphalt and concrete base pavement

ABSTRACT

Described herein are methods of improving the durability of concrete by the infusion of the concrete with a low-viscosity oligomeric solution, and subsequent curing of the oligomeric solution to form a high toughness polymer. Also described herein are compositions containing concrete and high toughness polymers, and formed articles made from concrete and high toughness polymers. The methods and compositions are useful for improving the durability of concrete roads and structures, as well as the durability of repairs to concrete roads.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of International ApplicationNo. PCT/US2012/035602 filed Apr. 27, 2012, which claims priority to U.S.application Ser. No. 13/096,750 filed Apr. 28, 2011, the disclosure ofwhich is incorporated herein by reference in its entirety. Thisapplication also is a continuation-in-part of U.S. application Ser. No.13/096,750 filed Apr. 28, 2011, which claims the benefit of U.S.Provisional Application No. 61/329,505 filed Apr. 29, 2010, thedisclosure of which is incorporated herein by reference in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with Government support of Grant No.70NANB10H019, awarded by the Department of Commerce—NIST. The Governmenthas certain rights in this invention.

BACKGROUND OF THE INVENTION

Damage to concrete structures such as roads, runways, bridges, and evenbuildings is a chronic problem around the world. The natural erosionprocesses in combination with pollution and/or heavy use have a severeimpact on the life of these structures.

Surface damage in concrete roads can result from a number ofcauses—frost damage, late finishing, toweling-on of a “topping” layerafter the main slab has been compacted and found to be low, ormechanical damage, caused for example by vehicles. Concrete can havehigh void content that can allow moisture to enter the surface and whenfrozen, produce tensile stresses that result in scaling and cracking ofthe surface. Additionally, concrete surfaces can scale as a result ofusing de-icing agents for ice and snow removal. The application of ade-icing agent to a pavement that is already covered in snow or ice willcause the surface to lose heat rapidly. This melts the ice on thesurface, but can cause freezing of any moisture that has become trappedin the material, potentially damaging it.

The occurrence of potholes on asphalt and cement pavements have beenlong standing issues for all transportation agencies in this country aswell as around the world. Over the years, improvements in materials,repair deployment methods, and supporting deployment systems havegreatly helped to make repairs more durable and economic. However, thelife of repaired potholes normally still is counted in terms of days ormonths, rather than years. The cost of pothole repair to the city andstate transportation and maintenance departments and federal agenciesare in the range of millions dollars per year. In addition, theexistence of potholes presents a great safety hazard to vehicles,structures, and pedestrians. A driver's inherent reaction to veer awayfrom a pothole often presents a danger to nearby vehicles andpedestrians and can cause serious traffic disturbances.

It is felt that the dominating mechanisms in forming potholes aredifferent under different weather or environment conditions, althoughthe presence of water in the sub-base serves as a major reason forpotholes formation. Potholes are generally caused by moisture and waterpercolates through fissures in pavement and collects in the sub-base ofthe pavement. In colder climates, the subsequent freeze-thaw actionpushes the pavement upward while traffic stresses the pavement and abreakdown of the road surface causes a material collapse that forms thepothole. Alternatively, in warmer areas, the freeze-thaw cycle plays aless important role. In places such as Florida, temperature and theimpact of water on the integrity of the road material and subsurfacecombine to reduce the integrity of the surface and lead to itscompromise. Additionally, traffic, poor construction, aged concrete, ora combination of these factors also play a role in all areas. Therefore,by limiting the amount of water that percolates through fissures in theroad or any subsequent repairs, the deleterious effects of moisture onroad quality can be mitigated.

It is felt that the failure and short life of the pothole repairs aredue to the creation of precursor cracks as the result of low toughness,low rutting resistance and low strength of the repairs materials. Themoisture further assisted the debonding of the binders within theaggregates within the repair material, and the repair materials with thebase of the pavement. Therefore, by increasing the dynamic toughness andstrength, and eliminate the voids that existed in the repair mixtureswhich provide paths for moisture penetration, the pothole repair lifecan be improved substantially.

Similarly, buildings, bridges and other concrete structures arecontinually impacted by weathering processes primarily catalyzed bywater. Water can cause spalling and damage to surfaces of bridges andbuildings, exposing structural components, such as steel beams andrebar, that may be further damages and cause even more erosion to theconcrete. Further, acid rain can not only cause ugly discoloration tobuilding facades, but also cause significant damage and deterioration toconcrete buildings, bridges, and other concrete surfaces, as the acidicsolution dissolves the calcium hydrates in the cement. As the currenthighway system in the United States is both vast and aging, there isclearly a need to find a way to cost-effectively protect the roads andbridges that make up our infrastructure.

On method that has been used for asphalt concrete is polymer modifiedasphalt (“PMA”). PMA has become common in road paving and roofing andmay represents much as 20% of all asphalt used today. Improvements inrutting resistance, thermal cracking, fatigue damage, stripping, andtemperature susceptibility have led polymer modified binder to besubstituted for asphalt in many paving applications, including hot mix,cold mix, chip seals, hot and cold crack filling, patching, and slurryseal. PMAs are used wherever performance and durability are desired.Asphalt specifiers are finding that many of the Superpave binder grades(Superpave, which stands for Superior Performing Asphalt Pavements,represents an improved, standardized system for specifying, testing, anddesigning asphalt materials) need polymer modification to meet all therequirements for high temperature rutting resistance and thermalcracking resistance at low temperatures.

A typical design of pothole repair is to raise the surface above that ofthe road surface, and to overlay the material directly over the roadsurface, around the perimeter of the repair. This is done to prevent theintrusion of water. Further, the overlaid area must be of sufficientthickness so that fractures do not occur, which can break and dislodgepieces of the repair. While it would be safer to make the repair flushwith the road surface, absent a firm watertight bond, this is notpossible. It would be desirable to produce a repair that does notproduce a bump that can adversely affect motorists. It would further bedesirable to have a repair material that does not compress with trafficso that it can be set at the desired height without fear of changingover time.

A typical practice with asphalt repair is to wait long enough for thematerial to cool sufficiently to harden enough to permit traffic. Thiscan result in long down-times that can be disruptive and costly. Itwould be an advantage to have a quick-curing thermoset that permits roadopening without damage in a relatively short time.

A typical design practice is to raise the pothole repair material abovethe road surface temporarily, and to count on traffic to reduce it toits desired final height. This can be difficult to estimate, as it canbe inexact how much the repair will settle, and in how much time.Weather can be an important variable here, as asphalt repairs settlemore and more quickly with heat. It can be appreciated that a repairthat ends up too high can cause an unsafe bump for motorists, and arepair that ends up too low can cause pooling of water. It would be anadvantage to have a repair material that does not appreciably changeafter its installation, simplifying the design and removing uncertainty.

Traditionally, polymers used for asphalt modification were typicallythermoplastic polymers that could be added to the mix as solids.Normally, such polymer addition involved adding the solid polymer,possibly after grinding, to a rear-shear mixing vessel containingasphalt generally heated above 325° F. for a period of time to assurethorough mixing. However, this tended to be a labor and capitalintensive process.

Despite the benefits of adding polymers to asphalt to improve physicaland mechanical performance, the polymers currently in use may notoptimize asphalt performance. Also, the cost of adding polymers to theasphalt at levels sufficiently high to meet desired specifications canbe prohibitive. As a result, the industry has looked for ways to enhancethe performance of the polymer modifiers, such as the development ofadditional chemical agents. Many of these agents have been termedcrosslinkers and are believed to either crosslink the polymer to theasphaltene component of the asphalt or crosslink the polymer and improveproperties. However, the incorporation of polymers and other componentsinto the asphalt can cause numerous problems that compromise therequisite asphalt properties. Further, these methods are incompatiblefor use with cement concrete. It is therefore desirable to developtechnologies and methods for adding polymers to concrete that produce aconcrete with improved durability that doesn't compromise the necessaryproperties of the material.

SUMMARY OF THE INVENTION

In accordance with one embodiment, the present invention is directed tomethods of increasing the durability of concrete and concrete structuresby incorporating polymers into the structure of the concrete. Theinfusion into the concrete of a low viscosity, fast curing oligomericsolution comprising a nanomolecular precursor and subsequentpolymerization of the monomer into a polymer with high toughnessprovides increased strength and durability to the concrete as well asproviding a barrier to the entry of moisture and chemicals that causedegradation of the surface.

In accordance with another embodiment, the present invention is directedto methods of increasing the durability of concrete and concretestructures by incorporating thermoset polymers into the structure of theconcrete. The infusion into the concrete of a low viscosity, fast curingoligomeric solution comprising a nanomolecular precursor and subsequentpolymerization of the monomer into a thermoset polymer with hightoughness provides increased strength to the concrete as well asproviding a barrier to the entry of moisture and chemicals that causedegradation of the surface. In some embodiments, the thermoset polymeris a polymer formed by ring opening methathesis polymerization. Specificexamples include polydicyclopentadiene and polynorbornene.

In accordance with another embodiment, the present invention is directedto compositions comprising concrete and polymers formed by ring openingmetathesis polymerization. The compositions of the embodiments of thepresent invention form highly durable materials that are resistant tomoisture intercalation and have improved resistance to degradationcaused by weather or use.

In accordance with another embodiment, the present invention is directedto formed articles comprising concrete and polymers formed by ringopening metathesis polymerization. Formed articles of embodiments of thepresent invention can be used, for example, in the building orreinforcement of structures, such as buildings or bridges, may be usedas structures or barriers to reinforce military or secure areas, forconcrete barriers on highways, or may be used as new or replacementsections of roads.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. Schematic illustration of aggregate-asphalt mix infiltrated withpolyDCPD to form a hardened continuous network within. While the figuredepicts asphalt concrete and its repairs, the method applies equally tocement concrete and its repairs.

FIG. 2. A dual layer structure with its top layer selectively reinforcedand with an oligomeric solution infiltrated to a depth less than anoverall thickness of the structure.

FIG. 3. Hamburg wheel-tracking device.

FIG. 4. a) Control D2 mix slab of about 320 mm (L), about 280 mm (W),and about 60 mm (H). b) Interface between top of about 1″ DCPDinfiltrated mix and about 1.5″ D2 mix. c) Interface between embeddedpavement beam with DCPD infiltration part.

FIG. 5. Rutting image comparison between tampered D2 mix and DCPDinfiltrated specimens (D2 mix has about 3000 passes, and DCPD specimenshave 20000 passes). a) Set #1, D2-1 (Lt.) and DCPD-2 (Rt.). b) Set #2,DCPD-3 (Lt.) and D2-4 (Rt.). c) Set #3, D2-2 (Lt.) and DCPD-1 (Rt.). d)Set #4, D2-3 (Lt.) and DCPD-4 (Rt.).

FIG. 6. Surface rutting of two layer structure (on the left) andinterface study (on the left).

DETAILED DESCRIPTION OF THE INVENTION Overview

In a first embodiment, the present invention comprises a method ofincreasing the strength and/or durability of concrete comprisinginfusing said concrete with a oligomeric solution having a viscosity ofless than about 200 cps and curing in less than about 24 hours,comprising a nanomolecular precursor, and optionally a solvent,optionally a catalyst, optionally an accelerator, and/or, optionally aninitiator; and forming a polymer having a toughness of greater than 6.0ft-lbs/in as measured by Notched Izod Impact Toughness.

In another embodiment, the nanomolecular precursor comprises an olefin,ester, urethane, imide, melamine, urea-formaldehyde, silicone, phenol,maleimide, or epoxide. In some embodiments, the nanomolecular precursorcomprises a cyclic olefin. In another embodiment, the nanomolecularprecursor comprises a cyclic olefin that undergoes ring openingmetathesis polymerization (“ROMP”). In another embodiment, thenanomolecular precursor comprises a five-, six-, seven-, eight-, nine-,ten-, or n-membered cyclic olefin that is bridged or unbridged, that mayinclude two or more fused rings, and undergoes ring opening metathesispolymerization, where n is an integer, such as in the range of 5 to 20,5 to 15, or 5 to 10. In another embodiment, the nanomolecular precursorcomprises a mixture of monomers, dimers, trimers, and/or tetramers ofcyclic olefins that undergo ROMP, and where the mixture of two or moreof these is used to control the reaction speed. In another embodiment,the nanomolecular precursor comprises a mixture of monomers, dimers,and/or trimers of cyclopentadiene (i.e., DCPD or C₁₀H₁₂) or norbornene(i.e., C₇H₁₀) and where the mixture of two or more of these is used tocontrol the reaction speed.

In another embodiment, the nanomolecular precursor comprises acombination of monomers, dimers, and/or trimers of a cyclic olefin withone or more additional monomer types. In some embodiments, theadditional monomer comprises an ester, an epoxy, and/or an olefin. Insome embodiments, the cyclic olefin comprises DCPD or norbornene. Insome embodiments, the cyclic olefin comprises DCPD. In some embodiments,the additional monomer comprises butadiene or ethylene.

In another embodiment, the oligomeric solution further comprises asolvent. In some embodiments the solvent is a non-aqueous solvent, Insome embodiments, the solvent is an organic solvent. In some embodimentsthe solvent is an alkene. Examples of alkenes include styrene, ethylene,and butadiene.

In some embodiments, the oligomeric solution further comprises acatalyst. In some embodiments, the catalyst is a ROMP catalyst. In someembodiments, the catalyst is a ruthenium or molybdenum catalyst. In someembodiments, the catalyst is a Grubbs-type catalyst. In someembodiments, the catalyst is a Schrock-type catalyst. In someembodiments, the catalyst is a Piers-type catalyst. In some embodiments,the catalyst is a Hoveyda-type catalyst. In some embodiments, thecatalyst is a Hoveyda-Grubbs-type catalyst. In some embodiments, thecatalyst is a “black box” catalyst. In some embodiments, the catalyst isa titanocene-based catalyst.

In another embodiment, the oligomeric solution further comprises anaccelerator, curing agent, inhibitor, and/or promoter. In someembodiments, additional additives may be present. Additional additivesthat may be present include, but are not limited to, processing aids,adhesion components, inorganic materials, fillers, and lubricants.

In another embodiment, the oligomeric solution has a viscosity nogreater than about 200 cps, 180 cps, 160 cps, 150 cps, 140 cps, 130 cps,120 cps, 110 cps, 100 cps, 90 cps, 80 cps, 70 cps, 60 cps, 50 cps, 40cps, 30 cps or 20 cps. In another embodiment, the oligomeric solutioncures in less than about 12 hours, less than 10 hours, less 8 hours,less than 6 hours, less than 4 hours, less than 2 hours, less than 1hours, less than 30 minutes, less than 15 minutes, less than 10 minutes,less than 5 minutes, less than 1 minute, less than 30 seconds, less than1 second, or about 1 second or less. Further, in another embodiment, theoligomeric solution cures in about 24 hours, 18 hours, 12 hours, 10hours, 8 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, 30minutes, 15 minutes, 10 minutes, 5 minutes, 2 minutes, 1 minute, 30seconds, 15 seconds, 10 seconds, 1 second, 0.5 seconds. In anotherembodiment, the oligomeric solution cures from about 1 minute to about24 hours, from about 1 minute to about 12 hours, from about 1 minute toabout 8 hours, from about 1 minute to about 6 hours, from about 1 minuteto about 4 hours, from about 1 minute to about 2 hours, from about 1minute to about 1 hour, from about 1 minute to about 30 minutes, fromabout 1 minute to about 15 minutes, from about 1 minute to about 10minutes, from about 1 minute to about 5 minutes, from about 10 minutesto about 24 hours, from about 10 minutes to about 12 hours, from about10 minutes to about 8 hours, from about 10 minutes to about 6 hours,from about 10 minutes to about 4 hours, from about 10 minutes to about 2hours, from about 10 minutes to about 1 hour, from about 10 minutes toabout 30 minutes, from about 30 minutes to about 24 hours, from about 30minutes to about 12 hours, from about 30 minutes to about 8 hours, fromabout 30 minutes to about 6 hours, from about 30 minutes to about 4hours, from about 30 minutes to about 2 hours, from about 30 minutes toabout 1 hour, from about 1 hour to about 24 hours, from about 1 hour toabout 12 hours, from about 1 hour to about 8 hours, from about 1 hour toabout 6 hours, from about 1 hour to about 4 hours, from about 1 hour toabout 2 hours, from about 2 hours to about 24 hours, from about 2 hoursto about 12 hours, from about 2 hours to about 8 hours, from about 2hours to about 6 hours, or from about 2 hours to about 4 hours.

In another embodiment, the polymer formed comprises a thermoset orthermoplastic polymer. In some embodiments, the polymer formed comprisesa thermoset polymer. In some embodiments, the polymer formed comprises athermoplastic polymer. In some embodiments, the polymer comprises acopolymer or a composite. In some embodiments, the copolymer orcomposite is a thermoset polymer. In some embodiments, the copolymer orcomposite is a thermoplastic polymer. In some embodiments, the polymeris a polyolefin, polyester, polyurethane, polyimide,poly(melamine-co-formaldehyde), poly(urea-formaldehyde), silicone,polyphenol, poly(maleimide-amide), epoxide, or polydicyclopentadiene. Insome embodiments, the polymer is formed from a cyclic olefin. In someembodiments, the polymer is a polymer formed by ROMP. In someembodiments, the polymer is polyDCPD. In some embodiments the polymer ispolynorbornene.

In another embodiment, the polymer has a toughness of at least about2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0 or 9.0 ft-lb/in as measured by NotchedIzod Impact ASTM D256. In some embodiments, the polymer has a toughnessof from about 2.0 ft-lb/in to about 10.0 ft-lb/in, from about 3.0ft-lb/in to about 10.0 ft-lb/in, from about 4.0 ft-lb/in to about 10.0ft-lb/in, from about 5.0 ft-lb/in to about 10.0 ft-lb/in, from about 6.0ft-lb/in to about 10.0 ft-lb/in, from about 7.0 ft-lb/in to about 10.0ft-lb/in, from about 5.0 ft-lb/in to about 12.0 ft-lb/in, from about 6.0ft-lb/in to about 12.0 ft-lb/in, from about 7.0 ft-lb/in to about 12.0ft-lb/in, or from about 8.0 ft-lb/in to about 12.0 ft-lb/in, as measuredby Notched Izod Impact ASTM D256.

In another embodiment, the concrete infused by the oligomeric solutioncomprises asphalt concrete or cement concrete. In some embodiments, theconcrete is asphalt concrete. In some embodiments, the concrete iscement concrete. In some embodiments, the asphalt concrete comprisesrecycled materials. In some embodiments, the recycled materials compriseautomobile tires. In some embodiments, the cement concrete comprisesPortland cement, Masonry cement, Mortar cement, gypsum, calciumaluminate cement, hydratable alumina, hydratable aluminum oxide,colloidal silica, silicon oxide, magnesia, limestone, hydrated lime,pozzolans, fly ash, granulated blast furnace slag, metakaolin, rice hullash, silica fume, oil well cementing grout, or hydraulic cement binder.In some embodiments, the cement concrete comprises Portland cement, flyash, slag cement or combinations thereof. In some embodiments, thecement concrete comprises recycled materials. In some embodiments, therecycled materials comprise recycled cement concrete.

In another embodiment, the concrete of the present invention is used inthe formation of a road or runway, a structural device or surface, anornamental device or surface, or a pre-formed article. In someembodiments, the concrete used comprises cement concrete. In someembodiments, the concrete used comprises asphalt concrete.

In another embodiment, the concrete of the present invention is used torepair a damaged surface. In some embodiments, the damaged surfacecomprises a concrete surface. In some embodiments, the damaged concretesurface comprises a cement concrete or asphalt concrete surface. In someembodiments, the damaged concrete surface comprises a road or runway. Insome embodiments, the damaged surface comprises a building or bridgesurface. In some embodiments, the surface comprises a pothole oralligator crack. In some embodiments, the repair material of the methodis approximately flush with the road surface instead of raised andoverlaid, and said repair material is bonded to the road material andsealed against the entrance of water. In some embodiments, the materialof the method is used to set the contour and height of the repair sothat subsequent traffic does not change it. In some embodiments, thematerial of the method is used to set the height and contour of therepair so that softness on hot days does not cause rutting by traffic.In some embodiments, the material of the method is used for fast curingso that the roadway can be opened to traffic in a short amount of time.

In another embodiment, the method of improving the durability ofconcrete comprises adding said oligomeric material to at least oneprecursor to said concrete. In some embodiments, the oligomeric materialis added to aggregate, then the oligomeric/aggregate mixture is combinedwith the asphalt or cement binder. In some embodiments, the oligomericmaterial is added to the binder, then the binder/oligomeric mixture iscombined with the aggregate. In some embodiments, the oligomericmaterial is added to the complete concrete mixture prior to deposition.

In some embodiments, the oligomeric material replaces the binder in theconcrete.

In some embodiments, the method comprises removal of material from apothole, subsequent cleaning of the pothole (typically with pressurizedair or water or another solvent), optionally spraying the oligomericsolution of the claimed invention into the pothole, filling said potholewith a concrete formulation, optionally waiting for concrete formulationto harden, spraying, pouring, or coating said concrete formulation withsufficient oligomeric solution to fill the voids in the material and/orprevent water from entering said concrete and/or increase the durabilityof the repair. In some embodiments, such as in the case of a potholerepair material including a mixture of asphalt and aggregates, nohardening or setting of the pothole repair material is required forinfiltration of an oligomeric solution. Rather, infiltration of thepothole repair material with the oligomeric solution can be carried outas soon as (e.g., immediately following or within a time interval ofabout 30 min or less, about 25 min or less, about 20 min or less, about15 min or less, about 10 min or less, or about 5 min or less) thepothole repair material is applied into a pothole and subjected to anydesired compaction to control a porosity level of the pothole repairmaterial. In some embodiments, the method comprises forming a dual layerstructure, such as within a pothole. The dual layer structure cancomprise a top layer or portion (e.g., with a thickness of about 5 cm orless, such as about 4.5 cm or less, about 4 cm or less, or about 3.8 cmor less), which is infiltrated by an oligomeric solution and reinforcedby a resulting polymer to a porosity level of about 5% or less (e.g.,about 4% or less or about 3% or less), and can comprise a bottom layeror portion (e.g., with the same or a different thickness), which isdeposited in the pothole first and then substantially compacted to aporosity level of about 8% or less (e.g., about 5% or less, about 4% orless, or about 3% or less). The viscosity of the oligomeric solution andthe porosity levels can be adjusted to control the extent ofinfiltration of the oligomeric solution such that the bottom layer mayor may not be reinforced by the resulting polymer. This dual layerstructure (with its top layer or portion selectively reinforced and withthe oligomeric solution infiltrated to a depth less than an overallthickness of the structure) has the advantages of lower polymericmaterials usage, lower cost for pothole patching, and reduced leaking ofpolymeric reinforcing materials to the bottom and sides of the pothole.The top layer has desirable properties including: (1) high toughness andstops crack initiation; (2) high strength to stop rutting and protectionfrom point loads; (3) impermeable to water and stops degradation andfreeze/thaw; (4) provides for some resin intrusion into the originalroad materials to soften the stiffness transition to the existing roadmaterial—this mitigates against cracks at the interface; and (5)optionally can have sand on its top surface, for slip reduction, colormatch with the road, and added UV resistance. The bottom layer hasdesirable properties including: (1) provides broad support to limitbending loads in the top layer; (2) cost effective and less resin used;(3) accepts some resin infusion for a softened interface with the toplayer and stops cracks at the interface; and (4) provides good stiffnessmatch and coefficient of thermal expansion match with the existing roadbed.

In another embodiment, the method comprises selectively depositing theoligomeric solution on concrete areas. Said selective deposition can bealong, for example, travel lanes, bus routes, truck routes, or otherareas that are heavily impacted and need additional durability, addingsaid oligomeric solution to said concrete prior to deposition of saidconcrete, spraying said oligomeric material on said concrete, or pouringsaid oligomeric material on said concrete.

In another embodiment, the present invention comprises a compositioncomprising a polymer formed by ROMP and concrete. In some embodiments,the concrete comprises asphalt concrete or cement concrete. In someembodiments, the polymer formed by ROMP comprises a cyclic olefin. Insome embodiments, the polymer formed by ROMP comprises polyDCPD orpolynorbornene. In some embodiments, the oligomeric solution forming thepolymer formed by ROMP comprises a nanomolecular precursor and has aviscosity of less than about 200 cps and cures in less than about 24hours. In some embodiments, the oligomeric solution forming the polymerformed by ROMP optionally includes solvent, optionally a catalyst,optionally an accelerator, and/or, optionally an initiator. In someembodiments, the composition further comprises additional polymers. Insome embodiments, the additional polymers form copolymers or compositeswith the polymer formed by ROMP. In some embodiments, the additionalpolymers are polyesters or epoxies. In some embodiments, the additionalpolymers form cyclic olefin copolymers with the polymer formed by ROMP.In some embodiments, the polymer formed by ROMP has a toughness ofgreater than about 4.0, 5.0 6.0, 7.0, 8.0 or 9.0 ft-lb/in as measured byNotched Izod Impact ASTM D256. In some embodiments, the polymer has atoughness of from about 2.0 ft-lb/in to about 10.0 ft-lb/in, from about3.0 ft-lb/in to about 10.0 ft-lb/in, from about 4.0 ft-lb/in to about10.0 ft-lb/in, from about 5.0 ft-lb/in to about 10.0 ft-lb/in, fromabout 6.0 ft-lb/in to about 10.0 ft-lb/in, from about 7.0 ft-lb/in toabout 10.0 ft-lb/in, from about 5.0 ft-lb/in to about 12.0 ft-lb/in,from about 6.0 ft-lb/in to about 12.0 ft-lb/in, from about 7.0 ft-lb/into about 12.0 ft-lb/in, or from about 8.0 ft-lb/in to about 12.0ft-lb/in, as measured by Notched Izod Impact ASTM D256.

In another embodiment, the present invention comprises a preformedarticle comprising concrete infused with a oligomeric solution having aviscosity of less than about 200 cps and curing in less than about 24hours, comprising a nanomolecular precursor, and optionally a solvent,optionally a catalyst, optionally an accelerator, and/or, optionally aninitiator; and forming a polymer having a toughness of greater thanabout 4.0, 5.0 6.0, 7.0, 8.0 or 9.0 ft-lb/in as measured by Notched IzodImpact ASTM D256.

In some embodiments, the present invention comprises a formed articlecomprising concrete and a polymer formed by ROMP. In some embodiments,the concrete comprises asphalt concrete or cement concrete. In someembodiments, the formed article comprises a component for use in thebuilding or reinforcement of structures, such as buildings or bridges.In some embodiments the formed article comprises a component for use asin structures or barriers to reinforce military or secure areas. In someembodiments the formed article comprises a component for use in concretebarriers on highways. In some embodiments the formed article comprises acomponent for use as new or replacement sections of roads.

In some embodiments of the formed article, the polymer formed by ROMPcomprises a cyclic olefin. In some embodiments, the polymer formed byROMP comprises polyDCPD or polynorbornene. In some embodiments, theoligomeric solution forming the polymer formed by ROMP comprises ananomolecular precursor and has a viscosity of less than about 200 cpsand cures in less than about 24 hours. In some embodiments, theoligomeric solution forming the polymer formed by ROMP optionallyincludes solvent, optionally a catalyst, optionally an accelerator,and/or, optionally an initiator. In some embodiments, the compositionfurther comprises additional polymers. In some embodiments, theadditional polymers form copolymers or composites with the polymerformed by ROMP. In some embodiments, the additional polymers arepolyesters or epoxies. In some embodiments, the additional polymers formcyclic olefin copolymers with the polymer formed by ROMP. In someembodiments, the polymer formed by ROMP has a toughness of greater thanabout 4.0, 5.0 6.0, 7.0, 8.0 or 9.0 ft-lb/in as measured by Notched IzodImpact ASTM D256. In some embodiments, the polymer has a toughness offrom about 2.0 ft-lb/in to about 10.0 ft-lb/in, from about 3.0 ft-lb/into about 10.0 ft-lb/in, from about 4.0 ft-lb/in to about 10.0 ft-lb/in,from about 5.0 ft-lb/in to about 10.0 ft-lb/in, from about 6.0 ft-lb/into about 10.0 ft-lb/in, from about 7.0 ft-lb/in to about 10.0 ft-lb/in,from about 5.0 ft-lb/in to about 12.0 ft-lb/in, from about 6.0 ft-lb/into about 12.0 ft-lb/in, from about 7.0 ft-lb/in to about 12.0 ft-lb/in,or from about 8.0 ft-lb/in to about 12.0 ft-lb/in, as measured byNotched Izod Impact ASTM D256.

DEFINITIONS

The following definitions apply to some of the aspects described withrespect to some embodiments of the invention. These definitions maylikewise be expanded upon herein.

As used herein, the singular terms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. Thus, forexample, reference to an object can include multiple objects unless thecontext clearly dictates otherwise. The use of the word “a” or “an” whenused in conjunction with the term “comprising” in the specification maymean “one,” but it is also consistent with the meaning of “one or more,”“at least one,” and “one or more than one.” The term “about” referencesall terms in the range unless otherwise stated. For example, about 1, 2,or 3 is equivalent to about 1, about 2, or about 3, and furthercomprises from about 1-3, from about 1-2, and from about 2-3.

The term oligomeric solution, as used herein, refers to the combinationof a nanomolecular precursor with optionally, a catalyst, initiator,inhibitor, solvent, accelerator, curing agent, or combination thereof,and may further include other monomers, dimers, trimers, or oligomersthat may polymerize by any means, or may include additionalthermosetting or thermoplastic polymers. Preferably, the oligomericsolution comprises the nanomolecular precursor, a catalyst, and,optionally, an inhibitor.

The term “concrete” as used herein, describes a hardened mixture of abinder and an aggregate. In the case of cement concrete, the hardenedmixture is typically formed by the chemical reaction of a binder withwater in the presence of the aggregate. Asphalt concrete comprises thecombination of asphalt as a binder with an aggregate to form athermoplastic composition. A structural surface, as used herein,describes a concrete surface along with the interior of the concretethat is accessible to the oligomeric solution wherein the surface ispart of a component of a building, concrete form, road, or the like thatis structural or load bearing component. A ornamental surface, as usedherein, describes a concrete surface along with the interior of theconcrete that is accessible to the oligomeric solution wherein thesurface is part of a component of a building, concrete form, road, orthe like that is primarily ornamental, aesthetically pleasing and/ornon-functional.

Binders include cements, such as Portland cement, Masonry cement, Mortarcement, and/or gypsum, calcium aluminate cement, hydratable alumina,hydratable aluminum oxide, colloidal silica, silicon oxide, magnesia,and may also include limestone, hydrated lime, pozzolans such as fly ashand/or granulated blast furnace slag, metakaolin, rice hull ash, andsilica fume or other materials commonly included in such cements, andmay also describe pastes, slurries, mortars, grouts, such as oil wellcementing grouts and hydraulic cement binder. Further, in the case ofasphalt cement, the binder is asphalt.

Aggregates in concrete play a dual role of acting as a filler andinfluencing the properties of the concrete material. Changes ingradation, maximum size, unit weight, and moisture content of theaggregate can all alter the character and performance of the concrete.Aggregates comprise as much as 60% to 80% of a typical cement concretemix, and are selected to be durable, blended for optimum efficiency, andproperly controlled to produce consistent concrete strength,workability, finishability, and durability. Aggregates as used herein,can include practically any material that meets these requirements forthe intended use, and include sand, crushed rock or gravel, recycledmaterials, and polymers.

Nanomolecular precursor, as used herein, refers to discrete moleculesthat will subsequently react to form the polymers of embodiments of thepresent invention. The nanomolecular precursors of embodiments of thepresent invention include monomers, dimers, trimers, or oligomers, orcombinations thereof. The nanomolecular precursors have a molecularlength along their longest dimension of about 100 nm or less, 90 nm orless, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nmor less, 30 nm or less, 20 nm or less, 10 nm or less, 5 nm or less, 4 nmor less, 3 nm or less, 2 nm or less, 1.5 nm or less, 1.2 nm or less, 1nm or less, 0.8 nm or less, or 0.6 nm or less, and down to about 0.4 nmor less. Alternatively, or in conjunction, the nanomolecular precursorshave a molecular length along their longest dimension of about 0.4 nm to100 nm, 0.4-90 nm, 0.4-80 nm, 0.4-70 nm, 0.4-60 nm, 0.4-50 nm, 0.4-40nm, 0.4-30 nm, 0.4-20 nm, 0.4-10 nm, 0.4-5 nm, 0.4-4 nm, 0.4-3 nm, 0.4-2nm, 0.4-1.5 nm, 0.4-1.2 nm, or 0.4-1 nm. Preferably, nanomolecularprecursors are cyclic olefins that undergo ROMP. Preferably,nanomolecular precursors comprise monomers, dimers, trimers, and/oroligomers of cyclic olefins that undergo ROMP. More preferably, thecyclic olefins are monomers, dimers, and/or trimers of cyclopentadieneor are norbornene. Most preferably, the cyclic olefins are monomers,dimers, and/or trimers of cyclopentadiene. Dicyclopentadiene, as usedherein, refers to both the chemical compound C₁₀H₁₂, as well as thetemperature dependent combination of the DCPD with it the monomercyclopentadiene.

The cyclic olefins of embodiments of the present invention may becombined with other monomers to form composites and/or copolymers. Theterm “cyclic olefins”, as used herein, includes monocyclic compounds,along with polycyclic (both bridged and unbridged), homocyclic, andheterocyclic compounds. For example, DCPD can be used in composites toimprove the performance of traditional unsaturated polyesters. In thesemodified polyester resins, the DCPD reacts with maleic acid and resultsin a higher T_(g) and more rapid development of acceptable hardness.DCPD has low viscosity, thus allowing a reduction in the total amount ofstyrene, resulting in a reduction in volatile emissions and polymershrinkage. DCPD also improves the cure of the resin when in an oxygenatmosphere, thus assisting in making the surface tack-free.

DCPD also can be used in the formation of epoxy composites. DCPD ispolymerized in the backbone and epoxy groups are still on the ends forcrosslinking. The addition of DCPD significantly improves the T_(g) ofthe epoxy, raising it from 160° C. at 22% concentration to 180° C. at28% concentration. Another modification to the formation of pure DCPDmonomer is the copolymer between DCPD and butadiene. This gives asignificant increase in toughness over what is already a tough polymer.Similar copolymers between DCPD and ethylene can be formed. TheDCPD/butadiene and DCPD/ethylene copolymers are referred to as cyclicolefin copolymers (COCs), and, unlike DCPD alone, are thermoplastic.

ROMP polymers, as used herein, refers to polymers that undergo ringopening metathesis polymerization. ROMP is a variant of the olefinmetathesis reaction. The reaction uses strained cyclic olefins toproduce stereoregular and monodisperse polymers and co-polymers. Thedriving force of the reaction is relief of ring strain in cyclic olefins(e.g. norbornene or cyclopentadiene) The addition of substituents to themonomer and the choice of solvent can alter the molecular weight of thepolymer produced.

The mechanism of the ROMP reaction involves an alkylidene catalyst andis similar to the mechanism of olefin metathesis with two importantmodifications. First, as the reaction involves a cyclic olefin, the“new” olefin that is generated remains attached to the catalyst as partof a growing polymer chain. The second difference is that the drivingforce for the ROMP reaction is the relief of ring strain. Therefore, thesecond step shown above is essentially irreversible. Olefins such ascyclohexenes or benzene have little or no ring strain and can not bepolymerized because there is no thermodynamic preference for polymerversus monomer. Strained cyclic olefins have sufficient ring strain tomake this process possible. Monomers based on norbornene derivatives areespecially popular as they can be readily synthesized from Diels-Alderreactions with cyclopentadiene.

The polymers produced in the ROMP reaction typically have a very narrowrange of molecular weights, something that is very difficult to achieveby standard polymerization methods such as free radical polymerization.The polydispersities (the weight average MW divided by the numberaverage MW) are typically in the range of 1.03 to 1.10. These molecularweight distributions are so narrow the polymers are said to bemonodisperse.

An important feature of this mechanism is that ROMP systems aretypically living polymerization catalysts. For example, one canpolymerize 100 equivalents of norbornene and then add a second monomerafter the first one is consumed. ROMP is a superior method for makingdiblock and triblock co-polymers and permits one to tailor theproperties of the resulting material. Such techniques are only possibleif the ratio of chain initiation and chain propagation are perfectlybalanced. Therefore, for functionalized monomers in particular, it isnot uncommon to try several different catalysts, solvents,concentrations, temperatures etc. to achieve the best results.

Solvent, as used herein, refers to those aqueous or non-aqueoussolutions that may be added to the oligomeric solution to obtain thedesired viscosity and/or other desired properties. Preferably, solventsare non-aqueous, organic solvents.

Catalysts, as used herein, are substances that modify and increase therate of a reaction without being consumed in the process. Catalysts ofembodiments of the present invention include those catalysts that willform polymers with the claimed criteria. Catalysts include ROMPcatalysts.

For some embodiments, catalysts of the present invention are ROMPcatalysts. ROMP catalysts include Grubbs-type catalysts, Schrock-typecatalysts, Piers-type catalysts, Hoveyda-type catalysts,Hoveyda-Grubbs-type catalysts, “black box” catalysts, andtitanocene-based catalysts. “Black box” catalysts refers toheterogeneous catalysts including a high valent transition metal halide,oxide or oxo-halide with an alkylating co-catalyst such as an alkyl zincor alkyl aluminum. Examples include WCl₆/SnMe₄ and Re₂O₇Al₂O₃.Titanocene-based catalysts refers to reaction of Cp₂TiCl₂ with twoequivalents of AlMe₃ to yield Cp₂Ti(μ-Cl)(μ-CH₂)AlMe₂, also calledTebbe's Reagent (Cp=ferrocene; Me=methyl). In the presence of a strongbase such as pyridine, the reagent is functionally equivalent to“Cp₂Ti═CH₂”. These Ti-based catalysts are typically not nearly as activeor tolerant of carbonyl functionalities as the later catalysts, butthese Ti complexes undergo stoichiometric Wittig-like reactions withketones, aldehydes and other carbonyls to form the correspondingmethylene derivatives. While these catalysts are exceedingly active,they typically have low tolerance for functional groups because of theirLewis acidic nature.

For some embodiments, catalysts of embodiments of the present inventionare ROMP catalysts that are air and moisture stable. Catalysts that meetthese criteria include Grubbs-type catalysts, and ruthenium andosmium-based catalysts.

Accelerator, as used herein, refers to a compound added to theoligomeric solution that increases the polymerization or curing rate.Inhibitor as used herein, refers to a compound added to the oligomericsolution that decreases the polymerization or curing rate.

Initiator, as used herein, refers to a compound that decomposes intofree radicals in the presence of monomers to begin a free radicalpolymerization process. Initiators may be used in conjunction with freeradical addition polymerization reactions.

Viscosity, as used herein, describes a measure of the resistance of afluid which is being deformed by either shear stress or tensile stress,and can relate to a dynamic viscosity of the fluid. In other words,viscosity describes a fluid's internal resistance to flow and may bethought of as a measure of fluid friction. Viscosity is measured withvarious types of viscometers and rheometers, and is measured incentipoise (cP).

Cure or curing, as used herein, refers to the toughening or hardening ofa polymer material by polymerization or monomers and/or cross-linking ofpolymer chains, brought about by chemical additives, ultravioletradiation, electron beam or heat. Generally, in the curing process, theresin viscosity drops initially upon the application of heat, passesthrough a region of maximum flow and begins to increase as the chemicalreactions increase the average length and the degree of cross-linkingbetween the constituent oligomers. This process continues until acontinuous 3-dimensional network of oligomer chains is created—thisstage is termed gelation. In terms of processability of the resin thismarks an important watershed: before gelation the system is relativelymobile, after it the mobility is very limited, the micro-structure ofthe resin and the composite material is fixed and severe diffusionlimitations to further cure are created.

Curing agents of embodiments of the present invention are substances ormixtures of substances added to the polymer composition to promote orcontrol the curing reaction. They may be reactive or catalytic. Areactive curing agent or hardener is generally used in much greateramounts than a catalyst, and is actually incorporated into the resultingpolymer. Promoters of embodiments of the present invention increasereactivity (shorter gel time and faster cure) of cure systems.

Thermoset, as used herein, is polymer material that irreversibly cures.A thermosetting polymer is a prepolymer in a soft solid or viscous statethat changes irreversibly into an infusible, insoluble polymer networkby curing. Curing can be induced by the action of a catalyst, heat orsuitable radiation, or a combination of two or more of these. A curedthermosetting polymer is called a thermoset.

Thermoplastic, as used herein, is a polymer that turns to a liquid whenheated to a sufficiently high temperature and freezes to a glassy statewhen cooled sufficiently. Most thermoplastics are high-molecular-weightpolymers whose chains associate through weak Van der Waals forces(polyethylene); stronger dipole-dipole interactions and hydrogen bonding(nylon); or even stacking of aromatic rings (polystyrene). Thermoplasticpolymers differ from thermosetting polymers in that they can be remeltedand remoulded. Many thermoplastic materials are addition polymers; e.g.,vinyl chain-growth polymers such as polyethylene and polypropylene.

Toughness, as used herein, is the measure of the energy a sample canabsorb without breaking or other deformation. Various methods have beendeveloped to quantify the toughness or impact resistance of polymers.There are two types of toughness—equilibrium toughness and impacttoughness. Equilibrium toughness is so named because the speed of thetensile test is usually so slow that equilibrium conditions can beassumed. Under these conditions, the toughness can be related to thearea under the stress-strain curve via integration of the curvedescribing the stress-strain. Generally, the toughness of a material ismore important under dynamic conditions, as when a force is appliedsuddenly. Therefore, impact toughness is defined as the energy absorbedby a material under sudden impact. Impact toughness is dependent uponthe ability of the material to internally deform. A number of tests havebeen developed to measure a materials impact toughness. These includethe Charpy impact test (ASTM D-6110), the Izod impact test (ASTM D-256),the tensile impact test (ASTM-1822), and the dart drop impact test (ASTMD-5628). The Izod impact test employs a sample fixed at one end with thependulum arm impacting the sample at the unsupported end with a notch onthe same side of the sample and the sample held just below the notch.

Formed article, as used herein, describes a concrete product cast in amold in a factory setting. Alternative terms include precast articles orpreformed articles. The advantages of a formed article are superiorquality control and mass production not achievable on site. Examplesincluded precast or pre-formed concrete walls, barriers, blocks, posts,beams, road sections, bridge components, railroad ties, junction boxes,grate inlets, culverts, swimming pools or sections of swimming pools,foundations, security or safe rooms, crypts, modular housing, housingcomponents (i.e., structural or aesthetic component that are integratedinto the structure of a house or apartment), specialty products,architectural forms, or sculptures.

Also, as used herein, the words “preferred,” “preferably,” and “morepreferably” refer to embodiments of the invention that afford certainbenefits, under certain circumstances. However, other embodiments mayalso be preferred, under the same or other circumstances. Furthermore,the recitation of one or more preferred embodiments does not imply thatother embodiments are not useful and is not intended to exclude otherembodiments from the scope of the invention.

Discussion

Embodiments of the present invention may be used to improve the strengthand/or durability of concrete in any situation. One particularapplication that is currently poorly addressed is that of potholerepair. The life of a repaired pothole is counted in days or monthsrather than in years. Pothole repair material, which normally compriseof discrete aggregates in a continuous phase of asphalt aftercompaction, can viewed as a structural composite. Therefore the shortlife of repaired potholes on asphalt-based pavements can be describedbelow in a sequence of failure: weak bonding between asphalt andaggregates; presence of interconnected voids in the asphalt-aggregatemix; moisture, or water, penetrates into the repaired area andintercalates through the asphalt-aggregate mix via the interconnectedvoids and weakens the bonds (stripping) between asphalt and aggregates;initiation of cracks in the repaired area and propagation through voidsor bond interfaces between asphalt and aggregates as the result oftraffic stresses; pull out, or raveling, of weakly bonded aggregatesfrom the asphalt phase from the surface and edge of the repair mixtureas the result of the compressive, shear, bending and tensile stressesexerted on the repaired region, caused by the traffic loading, with orwithout an overlay on top; development of hairline cracks at multiplesites and formation of inch-width cracks; separation of a portion or thewhole block of the repaired material from the original pothole follows;and finally, failure of the repaired region causes further damage to theedges of the original pavement and creates bigger potholes

In view of the above failure sequence of the asphalt-aggregate compositeand concrete-aggregate composites patching material for potholes, it isdesirable that a strong bonding material is developed for use in theaggregate-asphalt mix, or aggregate and other continuous phase matrixmaterials. Because of the conditions roads are continually subjected toand the specific steps that result in the failure of pothole repair, thefollowing properties are critical for a bonding material that couldprolong the life of a pothole repair:

-   -   1. Capable of infiltrating into the voids of a compacted        (throw-and-roll) or vibratory compacted (semi-permanent,        Spraying-injection) asphalt-aggregate mix.    -   2. Reduction of continuous and interconnected voids within the        aggregate composite mixture for increasing the strength of the        repair material and preventing the water/moisture infusion        through the thickness of the repair.    -   3. Reinforce the continuous phase of the aggregate composites by        replacing or enhancing the soft asphalt continuous phase, and        increases its strength and fracture toughness.    -   4. The “bonding” material should have one or more of the        following properties:        -   a. Compatible with asphalt.        -   b. Low viscosity for penetration into the asphalt-aggregate            mixture.        -   c. Controllable curing time (harden time) for field            application requirements.        -   d. Adjustable viscosity for penetration depth control.        -   e. High fracture toughness for energy absorbing without            breakage.        -   f. High compressive, shear and tensile strength.        -   g. Moisture and water resistant.        -   h. Moderate elongation.        -   i. Has the potential of being used as the binder with            aggregates. Variable viscosity if desired.        -   j. Can also be applied as sealing material at the edge of            the pothole repair.        -   k. Non-toxic and environmental friendly.        -   l. Ultra-violet resistance and ozone resistance.

In view of the above, embodiments described herein not only address thecriteria identified, but further, are generally applicable to allconcrete applications and provide improved durability and to both newand repaired concrete. Embodiments of the present invention can beapplied as a method for pavement pothole repair patching. The methodgenerally uses a low-viscosity oligomeric solution to infiltrate orinfuse into the concrete. The oligomeric solution is then allowed tocure into a polymer with high toughness. The oligomeric solutioncomprises a nanomolecular precursor along with additional optionalcomponents, such as catalysts, initiators, accelerators, inhibitors,curing agents, solvents, and the like. Preferably, the nanomolecularprecursors are cyclic olefins, and more preferably, the nanomolecularprecursors are cyclic olefins that undergo ROMP. Cyclic olefins thatundergo ROMP are desirable as they tend to have very low viscosities,have curing times that are controllable via the catalyst and oligomericsolution, and form incredibly tough polymers that retain theirdurability over the range of temperatures encountered under normal roaduse. Most preferably, the ROMP polymer is polyDCPD, optionally incombination with cyclopentadiene trimer. PolyDCPD is about 25% lessdense than epoxy but is much tougher, particularly at low temperatureswhere toughness becomes a design issue. In addition, as a dimer, thevery small rings (about 7 Å) slip over each other easily, resulting invery low viscosity; about that of water. DCPD and the cyclopentadienetrimer can be cured by a ROMP catalyst and be controlled by the amountof inhibitor and the cyclopentadiene trimer, from few seconds at roomtemperature, up to 24 hrs with heat cure. Further, the addition ofsubstituents to the monomer and the choice of solvent can alter themolecular weight of the polymer produced.

The ROMP process is quite useful because a regular polymer with aregular amount of double bonds is formed. The resulting product can besubjected to partial or total hydrogenation or can be functionalizedinto more complex compounds. Further, copolymers, block copolymers, andcomposites may be created by reaction of ROMP-formed polymers, such aspolyDCPD, with/subsequent to/prior to other ROMP-formed polymers, or byreaction in the presence of other types of polymers. The advantage toblock or mixed copolymers or composites is that it allows another levelof control with regard to the resulting polymers.

Additionally, for some embodiments, the strength and/or durability ofconcrete can be improved based on commercially-available ROMP-catalyzedpolymers. Some examples of polymers that can be produced through ROMPcatalysis are Vestenamer® or trans-polyoctenamer which is themetathetical polymer of cyclooctene; Norsorex® or polynorbornene; andTelene® and Metton®, which are polydicyclopentadiene catalysts producedin a side reaction of the polymerization of norbornene. Aruthenium-based catalyst produced by Materia, Inc. can be used as a ROMPcatalysts for certain embodiments.

The methods of embodiments of the present invention allow the oligomericsolution to quickly and thoroughly infuse into the concrete, and thensubsequently react. The infusion depth is a function of the void spacingin the concrete and the viscosity of the oligomeric solution. In thecase of asphalt concrete, infusion through the entire material ispossible. While not being bound by a specific theory, in asphaltconcrete, the cured polymer acts like a cage, filing the voids in theasphalt and tying these voids together. In pothole repair, this isadvantageous because it allows the fill material to essentially be“wired” into the old road surface via the polymer cage. Anotherembodiment is the use of cyclic olefins that diffuse into the existingroad material as well as the pothole repair material, bonding the twoand sealing against water penetration between them.

In the case of cement concrete, the infusion depth is dependent on thevoid spacing in the material, but is typically at least severalmillimeters. This infusion depth is sufficient to provide significantadditional toughness and improve the durability of the concrete bypreventing the intercalation of water into the concrete. While not beingbound by a specific theory, it is believed that the polymer forms acage-like form, connecting the voids in the concrete and sealing thesurface. One specific embodiment of the present invention is the use ofcyclic olefins that undergo ROMP, such as DCPD, for improving thedurability of aggregate-asphalt base pothole repair materials or anyaggregates that uses continuous binders including cements.

The polymer formed by embodiments of the present inventionadvantageously does the following:

1. Infiltrates the cold mixture of aggregate-asphalt, or neat aggregatein the form of a low viscosity liquid (oligomeric solution). Theaggregate-asphalt mix before the compaction, or even after the rollcompaction, still contains a high vol % of interconnected voids. Afterthe oligomeric solution has infiltrated, cured and hardened, it willform a continuous network (i.e., mechanical cage) around the discreteaggregates through the mixture's pre-existing voids. This continuousnetwork of structural cages can capsulate the aggregates with mechanicalforces and prevent the aggregates from being unraveled out from asphaltunder traffic stresses.

2. Forms a continuous mechanical cage network which will enable theprevention of moisture/water from sipping through the thickness of therepair material and mitigate its deleterious stripping effect onbonding.

3. Forms stronger bonds with aggregates than the bonds between asphaltand aggregates. (If the polymer is used as a single binder or a part ofthe binders with aggregates.)

4. Takes various types of traffic stresses and reduces the pull out ofaggregates which are the main components bearing traffic forces.

5. Distributes and transfers load more evenly and efficiently amongaggregates than the soft asphalt material

6. Takes elevated weather temperature without losing significantproperty degradation as asphalt does, due to its one-way thermosetpolymerization.

7. Applicable in field and on-site for various sizes of potholes andcracks on asphalt-base and concrete-base pavements

8. Applicable as an edge sealing material for the pothole repair. Theoligomeric solution can also penetrate the side walls and base of thesurrounding pavement due to its low viscosity. This provides anchoringforces for the repair material to the original pavement.

9. Displaces water, preventing it from eroding the concrete. PolyDCPDtypically does not undergo a phase change and has negligible contractionwith lowered temperatures.

10. Is catalyzed to exhibit a strong exotherm, which could be used withminimal heating (such as from a propane torch applied to the center ofthe installed patch) to create a chain reaction and cure the entirepatch.

A schematic of the infiltration of DCPD resin into the aggregate-asphaltcomposites is shown in FIG. 1. It shows the cured continuous cagednetwork of DCPD polymer holding the aggregates through the connectedvoids in a packed aggregate mixture. The DCPD polymer viscosity can beadjusted in order to reach the depth desired and be cured to hardenedstate within controlled time.

The oligomeric solution concentration can be adjusted to any percentagein the patching material mix and can be used for any of the current andfuture pothole repair processes including but not limited to:

1. Throw-and-go and throw-and-roll process

2. Spray injection

3. Edge seal of throw-and-roll

4. Semi-permanent

5. Cement pothole rapid patching process

6. Seal of alligator cracks or similar types of pavement discontinuousdefects

7. Pavement surface covers

The oligomeric solution can be applied via spray on the surface andsides of any of the patching methods listed above. It can also be usedas a premix with aggregates with or without asphalt or other types ofbinders.

Example

The following example describes specific aspects of some embodiments ofthe disclosure to illustrate and provide a description for those ofordinary skill in the art. The example should not be construed aslimiting the disclosure, as the example merely provides specificmethodology useful in understanding and practicing some embodiments ofthe disclosure.

Introduction

As the nation's asphalt pavements age and deteriorate, correctivemeasures are desired to restore safety and rideability increases. Thepotholes and alligator cracks in the asphalt pavement of our country'sroadways have become an annoying part of our daily life. An innovativeand integrated approach is developed for pothole repair technology, byusing a low-viscosity, tough dicyclopentadiene (DCPD) resin as a binderor additive in asphalt-aggregate pothole repair materials. Certainclasses of DCPD resin can be cured by commercially available catalysts(e.g., Grubbs' catalysts) to become an ultratough material with many ofthe desired properties for pothole repair.

To strengthen the pothole repair materials, the approach utilizes thelow viscosity characteristic of DCPD resin, which is controllable fromsimilar to water to very viscous, to infiltrate the asphalt-aggregatemixtures. The infiltration patterns and rates depend on the amount andpatterns of the interconnected voids within the asphalt-aggregates orneat aggregates. After the DCPD binder is infiltrated into theasphalt-aggregate mixtures, simultaneously cured and hardened undercontrolled conditions, it is expected that the cured DCPD, namely,polyDCPD, will form a continuous network of mechanical cages forcompacted asphalt-aggregates. The DCPD network may also preventmoisture/water from seeping through the thickness of the repair materialand mitigate moisture's deleterious stripping effect which weakens thebond strength between asphalt and aggregates. A stronger mechanical bondbetween the polyDCPD and aggregates may be formed which will preventaggregates from being stripped off under external forces.

Therefore, DCPD infiltration will not only increase the mechanicalproperties of pothole filling materials, such as rutting resistance,indirect tension strength, and Marshall stability, but increase thestrength of the bonding between filled materials with the originalpavement.

Hamburg Wheel-Tracking Rutting

The Hamburg Wheel-Tracking Device measures the combined effects ofrutting and moisture damage by rolling a steel wheel across the surfaceof an asphalt concrete slab that is immersed in hot water. The specimenscan be either of gyratory compacted cylinders or rolling wheel compactedslab. FIG. 3 shows the Hamburg wheel rutting machine and specimen slabin the sample holder.

Hamburg wheel rutting device has several advantages over Pine wheelrutting device and CPN wheel rutting device: 1) the tamper compactedslab can be directly measured with Hamburg wheel rutting device. If thePine wheel rutting device is used, a cylinder with about 6″ in diametertypically has to core from the tamper compacted asphalt slab, 2) thewheel of Hamburg rutting device runs a distance of about 230 mm onspecimen surface and is much longer than CPN wheel rutting device, inwhich a group of rotary wheels typically touch one spot. By running thewheel through the interface between pothole repair and the originalpavement, the interface failure mode can be estimated from this kindtest.

Specimen Preparation

As shown in Table 1, four kinds of specimens were prepared: 1) DCPDfully infiltrated D2 mix without fines, 2) control specimens withtampered D2 mix, 3) two-layer structure with about 1″ DCPD fullyinfiltrated D2 mix no fines on the top layer, and 4) interface betweenDCPD infiltrated in part with LA710 asphalt bar.

D2 mix was prepared with an asphalt mixer. Aggregates and sands weresieved through 0.5″, 0.375″, 0.25″, #4, #8, #18, #30, #50, and #200sieves and then made into a mix following Table 2. After heating up themix and mixed in the asphalt mixer, the hot D2 mix was poured into a panwith a size of about 18″ (L)×about 13″ (W)×about 4″ (H), and compactedwith a tamper by following a regular pothole repair procedure. After theasphalt cooled down in the pan, it was taken out and cut into the slabsize of about 320 mm by about 280 mm by about 60 mm (see FIG. 4 a).

After tampering this D2 mix in the pan, the interconnected void is about5-6% and can be less prone for DCPD infiltration. In order to increasethe porosity of the tampered mix and facilitate DCPD resin infiltrating,the #50 and #200 fines in the gradation curve were removed, and the tarbinder content is reduced from about 6.4% to about 4.5% in a weightratio. The infiltration process started when the mix is at the roomtemperature. The resin catalyzed with C827 was poured through thesurface. It took about 15-20 minutes for DCPD resin to cure inside. Thebulk was then taken out from the pan and cut into the same size as thecontrol ones shown in FIG. 4 a. The void in tampered D2 mix withoutfines is about 20-25%. After DCPD infiltration, the void is reduced toabout 4-8%. Total of 4 control specimens with D2 mix, and 4 DCPDinfiltrated specimens with D2 mix without fines were prepared.

One two-layer structure was prepared for rutting test. First, the D2 mixwas well tampered inside of the pan to a thickness of about 1.5″, andthen added D2 mix without fines and compacted to the thickness of about2.5″ total. Thus, the porous layer of D2 mix without fines is aroundabout 1″. DCPD was poured in and cured to form a two-layer structureshown in FIG. 4 b. Under UV, it can be seen that the DCPD infiltratedlayer is right above the well compacted D2 mix layer.

In order to evaluate the interface damage between DCPD infiltrated partwith the fully compacted asphalt pavement under the wheel running, onespecimen was prepared in which a fully compacted asphalt bar meeting thestandard of LA 710 highway was embedded inside of DCPD infiltrated D2mix with no fines. The damage around the interface during rutting testis closely observed. This specimen is shown in FIG. 4 c.

TABLE 1 Hamburg wheel rutting test metric Specimen Number Temperature D2mix 4 50° C. DCPD infiltrated D2 no fines 4 50° C. Interface test ofpavement beam 1 50° C. embedded in DCPD infiltrated D2 no finesInterface test of 1″ DCPD 1 50° C. infiltrated D2 no fines on 1.5″ D2mix

TABLE 2 D2 mix and D2 mix without fines (in weight ratio) 0.375″ 0.25″#4 #8 #18 #30 #50 #200 Tar D2   1%   14%   14% 16% 15.5% 15.5% 10% 14%6.4% D2 NF 1.3% 18.4% 18.4% 21% 20.4% 20.4% 0 0 4.5%

Results

The Hamburg wheel-tracking rutting test result is summarized in Table 3.From this table, it can be seen that all the tampered D2 mix failed atthe early stage of the test with the wheel passing no more than 3200.However, all of the DCPD infiltrated specimens easily passed the testwithout any noticeable rutting depth after 20000 passes.

TABLE 3 Summary of test results (control and DCPD mixes) Average Rut @20,000 Set Specimen Length Width Height Passes¹ No. Loc. Name (mm) (mm)(mm) (mm) 1 Lt. S1-LT-D2-1 321.2 259.3 67.6 >−19.3 @ 2,451 passes² Rt.S1-RT-DCPD-2 316.7 259.2 70.0 −0.14 2 Lt. S2-LT-DCPD-3 318.3 258.5 69.6−0.01 Rt. S2-RT-D2-4 321.2 261.0 68.3 >−19.9 @ 2,770 passes 3 Lt.S3-LT-D2-2 320.3 259.5 66.3 >−19.8 @ 3,102 passes Rt. S3-RT-DCPD-1 321.2259.3 66.4 +0.01 4 Lt. S4-LT-D2-3 319.0 261.7 62.4 >−19.0 @ 2500 passesRt. S4-RT-DCPD-4 318.3 258.0 63.4 −0.01 5 Lt. S5-LT-D2NF/ 315.7 259.370.9 −0.04 DCPD&D2NF Rt. S5-RT- 314.8 259.2 53.5 +0.02 INTERFACE Note:¹“−” downward rut depth; “+” upward rut depth; The average rut isdefined as the average of ruts at profile positions of 5, 6, and 7. ²Theaverage rut depth at 20,000 passes is greater than −19.3 mm rut whichoccurs at 2,451 passes.

The images of FIG. 5 show the surface rutting comparison between thetampered D2 mix and DCPD infiltrated D2 mix with no fines. All thetampered D2 mix specimens showed a deep rutting, while in the DCPDinfiltrated ones the rutting depth is barely seen.

In FIG. 6, the rutting performance of the two-layer structure is as goodas DCPD infiltrated 2″ specimens, even though it has about 1″ DCPDinfiltration depth on the top layer. The bottom supportive layer oftampered D2 mix has not been damaged or disintegrated during test. Sincea shallow layer of DCPD infiltration layer on the top can significantlyreduce the rutting tendency, this two-layer method can help to reducematerials cost while achieving a desired rutting performance.

On the right image of the FIG. 6, the wheel rutting depth is observed inthe two embedded asphalt bar, but not on the DCPD infiltrated part. Thisshowed DCPD infiltrated part is stronger and less rutting sensitive thanthe asphalt pavement bar. No interface delamination is observed, whichmeans the interface bonding with DCPD is strong and did not fail after20000 wheel passes.

CONCLUSION

With the Hamburg wheel-tracking device test, all the DCPD infiltratedspecimens showed supper rutting resistance, and easily passed the testwith negligible rutting depth. Even though DCPD infiltration layer inthe two-layer structure is thinner than the fully infiltrated ones, thetwo-layer structure specimen also showed a similar rutting resistance.In the embedded specimen, the interface bonding between DCPD infiltratedpart with the asphalt pavement bar is strong, and the asphalt bar showeda noticeable rutting depth.

While certain conditions and criteria are specified herein, it should beunderstood that these conditions and criteria apply to some embodimentsof the disclosure, and that these conditions and criteria can be relaxedor otherwise modified for other embodiments of the disclosure.

While the invention has been described with reference to the specificembodiments thereof, it should be understood by those skilled in the artthat various changes may be made and equivalents may be substitutedwithout departing from the true spirit and scope of the invention asdefined by the appended claim(s). In addition, many modifications may bemade to adapt a particular situation, material, composition of matter,method, or process to the objective, spirit and scope of the invention.All such modifications are intended to be within the scope of theclaim(s) appended hereto. In particular, while the methods disclosedherein have been described with reference to particular operationsperformed in a particular order, it will be understood that theseoperations may be combined, sub-divided, or re-ordered to form anequivalent method without departing from the teachings of the invention.Accordingly, unless specifically indicated herein, the order andgrouping of the operations are not limitations of the invention.Finally, the entire disclosures of all references cited in thisapplication are incorporated by reference.

What is claimed is:
 1. A method of repairing a road pavement,comprising: depositing a bottom layer of a pothole repair materialwithin a pothole of the road pavement; compacting the bottom layerwithin the pothole; depositing a top layer of the pothole repairmaterial over the bottom layer; infusing at least the top layer with aprecursor solution, wherein the precursor solution has a viscosity of nogreater than 100 cps, and cures in less than 2 hours; and forming athermoset polymer from the precursor solution, wherein the thermosetpolymer has a toughness of greater than 6.0 ft-lbs/in as measured byNotched Izod Impact ASTM D256.
 2. The method of claim 1, wherein thebottom layer is compacted to a porosity level of 8% or less.
 3. Themethod of claim 1, wherein the bottom layer is compacted to a porositylevel of 5% or less.
 4. The method of claim 1, wherein the bottom layeris compacted such that the top layer is selectively infused with theprecursor solution.
 5. The method of claim 1, wherein the precursorsolution is infused to a depth less than an overall thickness of the toplayer and the bottom layer.
 6. The method of claim 1, wherein athickness of the top layer is 5 cm or less.
 7. The method of claim 1,wherein the pothole repair material comprises a mixture of asphalt andaggregates.
 8. The method of claim 1, wherein the pothole repairmaterial comprises aggregates, and forming the thermoset polymercomprises forming a network of the thermoset polymer extending throughinterconnected voids among the aggregates.
 9. The method of claim 1,wherein the top layer is reinforced by the thermoset polymer to aporosity level of 5% or less.
 10. The method of claim 1, wherein theprecursor solution comprises a cyclic olefin.
 11. The method of claim10, wherein the cyclic olefin is dicyclopentadiene or norbornene. 12.The method of claim 1, wherein the precursor solution comprises a trimerof a cyclic olefin.
 13. The method of claim 1, wherein the precursorsolution comprises a ring opening metathesis polymerization catalyst.14. The method of claim 1, wherein the thermoset polymer is formed byring opening metathesis polymerization, and the thermoset polymercomprises polydicyclopentadiene or polynorbornene.
 15. The method ofclaim 1, wherein a top surface of the top layer is approximately flushwith a top surface of the road pavement.
 16. A dual layer structure forpothole repair, comprising: (a) a pothole repair material, wherein thepothole repair material comprises a mixture of asphalt and aggregatesarranged in a bottom layer and a top layer over the bottom layer; and(b) a thermoset polymer; wherein the thermoset polymer is infused intothe pothole repair material to form a network of the thermoset polymerextending through interconnected voids among the aggregates, and whereinthe network of the thermoset polymer extends to a depth less than anoverall thickness of the pothole repair material, and is localized inthe top layer of the pothole repair material.
 17. The dual layerstructure of claim 16, wherein a thickness of the top layer is 5 cm orless.
 18. The dual layer structure of claim 16, wherein the top layer isreinforced by the thermoset polymer to a porosity level of 5% or less.19. The dual layer structure of claim 16, wherein the thermoset polymercomprises polydicyclopentadiene or polynorbornene.
 20. The dual layerstructure of claim 16, wherein the thermoset polymer has a toughness ofgreater than 6.0 ft-lbs/in as measured by Notched Izod Impact ASTM D256.